Solar Energy Materials & Solar Cells 241 (2022) 111744

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Solar Energy Materials and Solar Cells

journal homepage: www.elsevier.com/locate/solmat

Thermophysical properties of LiF–LiCl–Li2CO3 eutectic mixture/

multi-walled carbon nanotubes for thermal energy storage
Zeyang Kang a, Jimin Xu a, Hui Liu a, Yuwen Lin b, Xiangyang Liu a, *, Maogang He a
a
Key Laboratory of Thermo–Fluid Science and Engineering, Ministry of Education, Xi’an Jiaotong University, Xi’an, Shaanxi Province, 710049, PR China
b
School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an, Shaanxi Province, 710072, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Latent heat thermal energy storage based on solid-liquid phase change material has a huge potential in dealing
Thermal energy storage with mismatch between energy demand and supply. LiF–LiCl–Li2CO3 ternary system was screened out for high
Thermophysical property temperature energy storage material due to its good thermophysical properties. Its eutectic composition (XLiF =
Composite phase change materials
28.41 mol%, XLiCl = 55.09 mol% and XLi2CO3 = 16.50 mol%) was predicted based on the developed thermo­
Eutectic salt
Nanoparticles
dynamic model and verified experimentally. The melting point, phase change latent heat, heat capacity, thernal
diffusivity, thermal conductivity and thermal stability of LiF–LiCl–Li2CO3 eutectic mixture were measured. And
the influence of the addition of multi-walled carbon nanotubes (MWCNTs) were analyzed. It was found that
adding MWCNTs could increase the latent heat, specific heat capacity, thermal diffusivity and thermal con­
ductivity of LiF–LiCl–Li2CO3 eutectic mixture, while didn’t significantly change the melting temperature.

1. Introduction thermophysical properties, the working temperature range, latent heat

Thermal energy storage is critical to deal with the mismatch between
energy supply and demand and meaningful to the effective utilization of
intermittent energy and waste heat. Among the three primary technol­
ogies generally being considered for thermal energy storage which are
sensible heat, latent heat and thermo-chemical thermal energy storage,
latent heat thermal energy storage (LHTES) is most promising owing to
the constant temperature during operation and large heat storage.
Molten salts exhibit desirable thermal characteristics such as the wide
operating temperature range, large latent heat, low vapor pressure and
good thermal stability, and thus being considered as potential solid-
liquid phase change materials (PCMs) for LHTES [1,2]. Solar Salt
(molar ratio of NaNO3–KNO3 is 64.1%: 35.9%) and HITEC Salt (molar
fraction of NaNO3–KNO3–NaNO2 is 6.6%: 41.9%: 51.5%) are two
commercial eutectic salts as thermal energy storage medium applied in
concentrated solar plants, but could only applied in the atmosphere of
low temperature due to the low molten temperature and poor thermal
stability. Developing competent salts for the application in medium or
high temperature thermal energy storage is urgent [3–7]. Pure com­
pound is hard to get a suitable phase change temperature for demand, so
multi-compound eutectic salts attracted a great deal of attention. To
screen eutectic salts which can work at high temperature and with good
of fusion and heat capacity of common salts are summarized in this work
[8], as shown in Fig. 1. LiF, LiCl and Li2CO3 were picked because of the
high latent heat of fusion, high heat capacity, wide working temperature
range and no chemical reaction between three components.
Moreover, the low thermal conductivity of the molten salts leads to
the low heat transfer rate during heat storage and release [9,10], which
is one drawback limiting the large-scale application of molten salts as
PCM [11–13]. Many works have been made to enhance heat transfer by
a variety of means, just like dispersing high thermal conductivity ma­
terials and encapsulating PCMs [14–17]. Han et al. [18] analyzed how
the dispersion behavior of Al2O3, CuO and ZnO nanoparticles influence
the thermophysical properties of a ternary eutectic salts
(MgCl2–KCl–NaCl with molar fraction of 51%: 22%: 27%, whose
melting point is 656 K), and concluded that the composite phase change
materials (CPCMs) with Al2O3 enhanced most compared to the other
nanoparticles, the average thermal diffusivity is increased by 62%. Tian
et al. [19] researched the effect of the addition of Mg particles on 43.6
mol% Li2CO3-31.4 mol% Na2CO3-25.0 mol% K2CO3 system (melting
point is 678 K), and found that thermal conductivity is greatly improved
with about 45%, but the latent heat of fusion is reduced about 6%. Yuan
et al. [20] focused on the simulation for the effect of charged
single-walled carbon nanotube on the heat capacity of carbonate salt

* Corresponding author.
E-mail address: lxyyang@mail.xjtu.edu.cn (X. Liu).

https://doi.org/10.1016/j.solmat.2022.111744
Received 18 January 2022; Received in revised form 28 March 2022; Accepted 11 April 2022
Available online 19 April 2022
0927-0248/© 2022 Elsevier B.V. All rights reserved.
Z. Kang et al. Solar Energy Materials and Solar Cells 241 (2022) 111744

2. Thermodynamic model

2.1. Gibbs energy for pure salt

The Gibbs energies of LiF, LiCl and Li2CO3 can be expressed as the
function of temperature which is expressed as

Gφ0 = Gφ (T) − H RER = a + bT + cT ln(T) + dT 2 + eT 3 + fT − 1

(1)

where Gφ0 (T) is the Gibbs energy function in φ phase, HRER is the molar
enthalpy at 298 K at reference state, a, b, c, d, e and f are coefficients, and
T is the temperature in Kelvin. Table 1 displays the equations for the
Gibbs energy of pure salts which are fitted by the data in literature [8].

2.2. Gibbs energies for binary system

The substitutional solution model was used to model the Gibbs en­
ergies of LiF–LiCl, LiF–Li2CO3 and LiCl–Li2CO3 systems in liquid phase.
The expression of Gibbs energy is given as:

(2)
φ φ
Gφ = ref G + id G + ex Gφ
∑
ref φ
G = x0i Gφi (3)
i

∑
(4)
id φ
G = RT xi ln(xi )
i

where ref G is the contribution from pure components in φ phase to the

φ

Gibbs energy, id G is the ideal mixing contribution and ex Gφ is the

φ

contribution from non-ideal interactions between pure components, also

known as the excess Gibbs energy. The Redlich-Kister [25] form is
commonly used to represent the excess Gibbs energy in the CALPHAD
method, which is written as
∑ φ
ex φ
G = xi xj v
Li.j (xi − xj ) (5)
v

where xi is the mole fraction of the component i, and v Lφi.j is the

parameter of the binary interaction in v order.

2.3. Thermodynamic optimization of binary systems

A series of self-consistent thermodynamic model parameters was

Fig. 1. Summary of the properties of salts (~K means there is no data in established based on experimental phase equilibria data of the LiF–LiCl,
literature for upper limit) [8]. LiF–Li2CO3, LiCl–Li2CO3 binary systems which was taken from Factsage
[26]. All thermodynamic model parameters obtained in this work are
(28.57 mol % Li2CO3-71.43 mol% K2CO3 with melting point of 771 K, listed in Table 2.
34.83 mol% Li2CO3-65.17 mol% K2CO3 with melting point of 776 K, The phase diagrams of the LiF–LiCl, LiF–Li2CO3, LiCl–Li2CO3 binary
46.59 mol% Li2CO3-53.41 mol% K2CO3 with melting point of 761 K), systems were calculated based on the thermodynamic model parameters
and found an increase about 16% in heat capacity. Wang [21] et al. obtained in Table 2. And the phase diagrams are shown in Figs. 2–4, The
researched the effects of functionalized multi-walled carbon nanotubes calculated eutectic points of three LiF–LiCl, LiF–Li2CO3, LiCl–Li2CO3
(MWCNTs) on thermophysical properties of liquid polyethylene glycol
8000, it was found the nanocomposite PCM showed excellent increment Table 1
on thermal conductivities with the addition of MWCNTs. Thermodynamic properties of pure compounds.
In the present work, the eutectic mixture of LiF–LiCl–Li2CO3 is pre­ Phase T/K Gibbs energy (J/mol) Ref.
dicted using CALPHAD (Calculation of Phase Diagram) method based on LiCl S 298–883 − 421787.8 + 228.1512T-41.90221TlnT- [8]
the thermodynamic evaluation and optimization on its subsystems 0.01137310T2
[22–24]. Then, the composites consisting of LiF–LiCl–Li2CO3 eutectic L 298–1700 − 417234.5 + 422.3922T- [8]
salt and various mass fractions of MWCNTs from 0.2 wt%, 0.5 wt%, 1 wt 73.38010TlnT+0.004740050T2
LiF S 298–1123 − 629355.4 + 225.6422T–37.97422T⋅lnT- [8]
% to 2 wt% were prepared. The effect of MWCNTs on the eutectic point,
0.01112880T2
phase change latent heat, heat capacity, thermal diffusivity, thermal L 298–2000 − 617804.9 + 386.9808T-64.18498TlnT [8]
conductivity and thermal stability of LiF–LiCl–Li2CO3 eutectic salt are Li2CO3 S1 298–623 − 1252974 + 718.0553T-120.1194TlnT [8]
experimentally investigated. S2 623–683 − 1273698 + 985.4408T-156.5140TlnT [8]
S3 683–993 − 1279481 + 1050.291T-165.1579TlnT [8]
L 298–2000 − 1253215 + 1163.763T-185.4357TlnT [8]

S: solid phase L: liquid phase.

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Z. Kang et al. Solar Energy Materials and Solar Cells 241 (2022) 111744

Table 2
Binary thermodynamic parameters for the LiF–LiCl–Li2CO3 subsystems.
Subsystems Phase type Phase name Thermodynamic parameters (J/mol)

LiF–LiCl Solution Liquid 0 L

LLiF,LiC1 = 872.956–2.50411T
1 L
LLiF,LiC1 = -2332.35–4.06720T
LiF–Li2CO3 Solution Liquid 0 L
LLiF− Li2 CO3 = -18113.6 + 19.9518T
1 L
LLiF− Li2 CO3 = 1602.11–1.1919T
LiCl– Li2CO3 Solution Liquid 0 L
LLiC1− Li2 CO3 = 35713.2–47.7572T
1 L
LLiC1− Li2 CO3 = 33651.9–38.5628T

Fig. 4. Calculated phase diagram of LiCl– Li2CO3 in comparison with experi­

mental data [26].

2.4. Thermodynamic optimization of ternary systems

The phase diagrams and thermodynamic model parameters of

Fig. 2. Calculated phase diagram of LiF–LiCl in comparison with experimental
data [26].
LiF–LiCl, LiF–Li2CO3, LiCl–Li2CO3 binary systems were used to predict
the phase diagram of LiF–LiCl–Li2CO3 ternary system by the foundation
of the Kohler-Toop technology [6]. Fig. 5 displays the calculated liq­
uidus projection of LiF–LiCl–Li2CO3 ternary salt. The predicted eutectic
point of LiF–LiCl–Li2CO3 ternary system is 735 K with XLiF = 28.41 mol
%, XLiCl = 55.09 mol% and XLi2CO3 = 16.50 mol%. The experiment will
be done in the following section to verify the predicted eutectic point.
3. Experiment

3.1. Materials

3.1.1. Preparation of ternary eutectic salt

The pure salts used in this work were LiF (99.99%, Aladdin, CAS:
7789-24-4), LiCl (99%, Aladdin, CAS: 7447-41-8) and Li2CO3 (99.99%,

Fig. 3. Calculated phase diagram of LiF–Li2CO3 in comparison with experi­

mental data [26].

binary systems are located at 772 K and 30.1 mol% LiF-69.9 mol% LiCl,
886 K and 48.1 mol% LiF-51.9 mol% Li2CO3, and 789 K and 69.0 mol%
LiCl-31.0 mol% Li2CO3, respectively. The calculated results show great
agreement with the experiment data [26], the deviations of eutectic
temperatures are 0.5 K, 0.2 K, 1 K, respectively.

Fig. 5. Calculated phase diagram of LiF–LiCl–Li2CO3 system.

3
Z. Kang et al.
Aladdin, CAS: 554-13-2). Ternary eutectic salt was prepared by
weighting method using electronic analysis balance. The mixture is
heated to 823 K and held for 40 min using a muffle furnace under an
argon atmosphere then cooled down to the room temperature and
repeated this process thrice to obtain the well-mixed salt.
3.1.2. Preparation of CPCMs
MWCNTs (99.9% purity, 10–30 μm, Aladdin, CAS:308068-56-6) was
selected as heat-transfer-enhancement additives and dispersed into the
prepared LiF–LiCl–Li2CO3 ternary salt to synthesize CPCM. To liquefy
the mixture, the mixtures were heated at a constant heating rate of 5 K/
min from 298 K to 823 K in a muffle furnace, and then held for 600 min
to disperse MWCNTs particles into the entire molten salts.
3.2. Characterization
3.2.1. Micro-structure analysis
The scanning electron microscope (SEM, Regulus 8100, Hitachi) was
used to obtain the surface microscopic morphology of the ternary
eutectic salt, MWCNTs, and CPCMs at 298 K. The 20-kV accelerating
voltage and 8.5 nm resolution of the instrument were set, respectively.
3.2.2. Thermophysical property
The melting point and phase change latent heat of the ternary
LiF–LiCl–Li2CO3 eutectic salt and its CPCMs were measured by DSC (STA
449 F5 Jupiter, NETZSCH, Germany). The atmosphere of the DSC ex­
periments was proceeded under nitrogen, with the flow rate of 40 mL/
min. The heating rate was 10 K/min from 298 K to 1273 K. The
Fig. 6. SEM images of the pure salts and nanofluids.
4
Solar Energy Materials and Solar Cells 241 (2022) 111744
uncertainty of temperature was within 3 K [27,28] and the relative
uncertainty of phase change latent heat is approximated to be in 4%.
The specific heat capacity of the ternary LiF–LiCl–Li2CO3 eutectic
salt and its CPCMs were also measured by the DSC (STA 449 F5 Jupiter,
NETZSCH, Germany). During the measurement, sapphire was taken as
the standard substance. The measurements were all under the protection
of nitrogen atmosphere with heating rate of 10 K/min, and the flow rate
of the gas is maintained at 40 mL/min.
Laser flash analysis (LFA 467, NETZSCH, Germany) was used to
measure the thermal diffusivity of the ternary eutectic salt and its
CPCMs in the nitrogen atmosphere at 298 K. The uncertainty of the
thermal diffusivity is estimated at 5% [17,29]. Two-times experiment
was run for each sample.
3.2.3. Thermal stability
The thermogravimetric analysis (TGA) was used to measure the
thermal stability of the ternary eutectic salt and its CPCMs. The TGA
tests from 303 K to 1273 K were carried out using the simultaneous
thermogravimetric-differential scanning calorimetry (STA 449 F5
Jupiter, NETZSCH, Germany) in a 40 mL/min nitrogen flow with a
heating rate of 10 K/min. The temperature uncertainty was about 0.5 K.
The weighing uncertainty is about 0.1 μg [30].
4. Results and discussion
4.1. Microstructure analysis
The MWCNTs are coaxial tubes composed of hexagonal carbon atoms
Z. Kang et al.
in the arrangement of several to dozens of layers. The radial and axial
sizes of MWCNTs is at the nanometer and micron scales, with the inner
diameter of 5–10 nm, outer diameter of 10–20 nm and the length of
10–30 μm, respectively. The SEM image of MWCNTs is shown in Fig. 6
(a). Fig. 6 (b,c) are the SEM images of the LiF–LiCl–Li2CO3 eutectic salt
and the CPCMs respectively, and the result in Fig. 6(c) demonstrates that
MWCNTs disperse into salts in various types, just like inlaid, penetration
and package, the microstructure of the salts with MWCNTs nanoparticle
is possibly formed through the combined effects of heteronuclear so­
lidification and electrostatic interactions [31].
4.2. Thermophysical property of LiF–LiCl–Li2CO3 salt/MWCNTs
composite salt
4.2.1. Melting temperature
The DSC curves of the LiF–LiCl–Li2CO3 base salt and the CPCMs
which dispersed with different mass fraction of MWCNTs were displayed
in Fig. 7 (a). Only one single peak could be found in the DSC curve,
which manifests that the prediction for the phase diagram is precise.
And the melting point of the LiF–LiCl–Li2CO3 base salt is 730 K, which
shows great agreement with the calculated value (735 K) in section 2.4.
The melting temperatures of the LiF–LiCl–Li2CO3/CPCMs change
negligibly with the increasing mass fraction of MWCNTs, and displayed
in Fig. 7 (b), the biggest temperature difference (with 0.5 and 1 wt%
Fig. 7. The eutectic point of LiF–LiCl–Li2CO3 base salt and CPCMs.
5
Solar Energy Materials and Solar Cells 241 (2022) 111744
MWCNTs) for the onset temperature is only 1.0 K, 2 K for peak tem­
perature and 3 K for end temperature.
4.2.2. Specific heat capacity
Specific heat capacities of the LiF–LiCl–Li2CO3 base salt and CPCMs
were calculated from ambient temperature to 1273 K. As shown in
Fig. 8, the average specific heat capacity is 2.38 J/(g⋅K)-1 at the tem­
perature range from 573 K to 713 K (solid state). The average specific
heat capacity is 2.70 J/(g⋅K)-1 for the temperature range from 753 K to
873 K (liquid state). Adding MWCNTs can increase the heat capacity of
LiF–LiCl–Li2CO3 eutectic salt, but overmuch MWCNTs will weaken the
improvement. Nanomaterials have large specific surface area, which
contributes to the formation of the nano-layer, the nano-layer will in­
crease the specific heat capacity of the CPCM, meanwhile, the larger
specific surface area leads to the larger surface energy, which accelerates
the aggregation of the nanomaterials, finally causes the reduction of the
specific surface area, and the effect of nanomaterials on the specific heat
capacity of CPCM are depending on these two factors, the specific heat
capacity of CPCM increases when the effect of the former is greater than
the latter, the specific heat capacity decreases when the effect of the
former is less than that of the latter. The increment caused by 0.2 wt%,
0.5 wt%, 1 wt%, and 2 wt% MWCNTs, are 33.33%, 20.20%, 12.47% and
− 1.65% for liquid state.
4.2.3. Latent heat
Fig. 9 shows the experimental data of the latent heat of the
LiF–LiCl–Li2CO3 eutectic salt and its CPCMs. The latent heat of
LiF–LiCl–Li2CO3 eutectic salt and its CPCMs are 408 kJ/kg
(LiF–LiCl–Li2CO3 eutectic salt), 492 kJ/kg (LiF–LiCl–Li2CO3 eutectic
salt+0.2 wt% MWCNTs), 504 kJ/kg (LiF–LiCl–Li2CO3 eutectic salt+0.5
wt% MWCNTs), 482 kJ/kg (LiF–LiCl–Li2CO3 eutectic salt+1 wt%
MWCNTs), 442 kJ/kg (LiF–LiCl–Li2CO3+2 wt% MWCNTs), All of the
latent heat of the CPCMs are higher than eutectic salt [32]. The incre­
ment is 20.59% (0.2 wt% MWCNTs), 23.53% (0.5 wt% MWCNTs),
18.14% (1 wt% MWCNTs) and 8.33% (2 wt% MWCNTs). These results
imply that the MWCNTs have a contribution on the latent heat. The
more MWCNTs added, the more nucleation crystallization of the base
salt in the MWCNTs, thus, reducing the phase separation degree, and the
latent heat will increase.
4.2.4. Thermal diffusivity
The thermal diffusivity of the LiF–LiCl–Li2CO3 eutectic salt and
CPCMs measured by LFA are shown in Fig. 10(a). The thermal diffusivity
Fig. 8. The heat capacity of LiF–LiCl–Li2CO3 base salt and CPCMs.
Z. Kang et al.
Fig. 9. Latent heat of LiF–LiCl–Li2CO3 eutectic salt and CPCMs.
Fig. 10. Thermal diffusivity of LiF–LiCl–Li2CO3 eutectic salt and its CPCMs.
of the eutectic salt (1.227 mm2/s) decreases with 0.2 wt% MWCNTs
(1.006 mm2/s), then is maximized at 0.5 wt% (1.362 mm2/s), the
thermal diffusivity of the CPCMs was greatly improved. The thermal
diffusivity of the CPCMs decreases first which may be caused by the high
interface thermal resistivity of MWCNTs when the little MWCNTs is
added, the CPCM don’t form the thermal conductive network, the high
interface thermal resistivity between MWCNTs and base salt would
cause the thermal diffusivity of the composites lower than base salt.
Meanwhile, the anisotropy of local heat transfer between the base salt
and MWCNTs was larger, it also affected the heat transfer capacity of the
system. With more addition of MWCNTs, the thermal conductive
network forms, and results in high heat transfer rate, while the later
decrease is caused by the aggregation of MWCNTs, and the heat transfer
between MWCNTs and base salt was prevented which attenuate the
enhancement effect of nanomaterials [33–36].
4.2.5. Thermal conductivity analysis
The thermal conductivity could be obtained by equation (7).
κ = α⋅ρ⋅Cp (7)
where κ is the thermal conductivity, α is the thermal diffusivity, ρ is the
6
Solar Energy Materials and Solar Cells 241 (2022) 111744
density, and Cp is the specific heat.
Equation (8) could be used to calculate the density of the CPCMs
[37].
ρCPCMs = φnp ⋅ρnp + (1 − φnp )⋅ρsalt (8)
where φnp is the concentration of MWCNTs, ρCPCMs, ρnp and ρsalt are the
density of CPCMs, MWCNTs, and LiF–LiCl–Li2CO3 eutectic salt.
The empirical correlations of density with temperature for LiF, LiCl
and Li2CO3 are fitted by the data in literature [38] and shown in Table 3.
Assuming that the density of MWCNTs is constant due to its negligibly
alter with temperature.
The specific heat capacity of LiF, LiCl, Li2CO3 salt and MWCNTs were
obtained from literature [8,39], the specific heat capacity of CPCMs can
be obtained via the following equation [40].
φnp ⋅ρnp ⋅Cp, np + (1 − φnp )⋅ρsalt ⋅Cp, salt
Cp, CPCMs = (9)
ρCPCMs
where Cp,CPCMs, Cp,np, and Cp,salt are the specific heat capacity of CPCMs,
MWCNTs and LiF–LiCl–Li2CO3 eutectic salt, respectively. Detailed
values of the specific heat capacity of LiF, LiCl, Li2CO3 salt, MWCNTs
and LiF–LiCl–Li2CO3 eutectic salt at room temperature are shown in
Table 4. Consequently, the thermal conductivity of the LiF–LiCl–Li2CO3
eutectic salt and CPCMs were calculated via Equation. (9) and displayed
in Fig. 11. The thermal conductivity of the LiF–LiCl–Li2CO3 eutectic salt
and CPCMs are 3.144 W⋅m-1⋅K-1 (base salt), 2.753 W⋅m-1⋅K-1 (0.2 wt%
MWCNTs), 3.563 W⋅m-1⋅K-1 (0.5 wt% MWCNTs), 3.422 W⋅m-1⋅K-1 (1 wt
% MWCNTs), 2.682 W⋅m-1⋅K-1 (2 wt% MWCNTs),.
The average thermal conductivity of CPCMs were increased
compared with the thermal conductivity of the LiF–LiCl–Li2CO3 ternary
eutectic salt, which caused by the high thermal conductivity of
MWCNTs, it makes the CPCMs form effective heat conduction links.
Furthermore, the MWCNTs could also impel the CPCMs to form nano­
structures, which will reduce the heat transfer rate [17]. Tao [13] stated
that the aggregation of nanomaterials and the thermal contact resistance
between different materials can reduce the thermal conductivity, so it is
vital to take these factors into consideration when analyzing the influ­
ence of different nanomaterials on the thermal conductivity of base salts.
Therefore, it can be considered that for CPCM in this work, the effect of
forming thermal conduction link on improving thermal conductivity is
greater than the effect of contact thermal resistance and nanomaterial
aggregation when the mass fraction of MWCNTs is at the range from 0.5
wt% (3.56 W/m⋅K with 13.43% enhancement)-1 wt% (3.42 W/m⋅K with
8.94% enhancement), and the opposite force will appear at 0–0.2 wt%
(2.75 W/m⋅K with 12.35% decrement) and at 2 wt% (2.68 W/m⋅K with
14.6% decrement). In particular, the enhancement for the thermal
conductivity of LiF–LiCl–Li2CO3 based CPCMs has a most significant
increase at 0.5 wt% MWCNTs.
4.2.6. Thermal stability
Thermal stability of LiF–LiCl–Li2CO3 eutectic salt and its CPCMs
were measured using TGA apparatus in nitrogen atmosphere. Thermal
stability determines the upper-limit working temperature of thermal
energy storage materials. As shown in Fig. 12, the thermal stability of
the salts mentioned above were determined experimentally from 298 K
to 1273 K. Results pointed out that the weight change of
LiF–LiCl–Li2CO3 eutectic salt and its CPCMs with 0.2 wt%, 0.5 wt%, 1 wt
% and 2 wt% MWCNTs are 2.7%, 2.3%, 1.6%, 4.3% and 7.3% at the
Table 3
Densities of single-component salt [38].
Salt Density equation (g/cm3)
LiF ρ = 2.3581–4.902⋅10-4 T
LiCl ρ = 1.8842–4.328⋅10-4 T
Li2CO3 ρ = 2.2026–3.729⋅10-4 T
Z. Kang et al. Solar Energy Materials and Solar Cells 241 (2022) 111744

Table 4 experiment, the LiF–LiCl–Li2CO3 eutectic salt was placed in graphite

Specific heat of single-component salt, base salt, and CPCMs at room boats and then heated in muffle furnace from room temperature to 923 K
temperature. in nitrogen atmosphere at a constant heating rate of 20 K/min, and then
Salt Specific Salt Specific kept for 600 min. After melting in the furnace, the sample was cooled to
heat Cp(J/ heat Cp(J/ room temperature and the temperature change of the salt was recorded.
g⋅K) g⋅K) Three cycles have been completed, and the weight changes after three
LiF 1.6147 LiF–LiCl–Li2CO3 ternary 1.331 cycles are almost same, the weight loss should be caused by the loss of
eutectic salt + 0.2 wt% water, as shown in Table 5.
MWCNTs
After that, DSC-TG tests were carried out on LiF–LiCl–Li2CO3 which
LiCl 1.133 LiF–LiCl–Li2CO3 ternary 1.349
eutectic salt + 0.5 wt% have kept in muffle furnace for 600 min, 1200 min and 1800 min,
MWCNTs respectively, and the results are shown in Fig. 13. As can be seen from
Li2CO3 1.303 LiF–LiCl–Li2CO3 ternary 1.379 the Fig. 13(a), during the test, the mass of all molten salt is basically no
eutectic salt + 1 wt% loss. The three heating curves of DSC tests indicate that the phase
MWCNTs
LiF–LiCl–Li2CO3 1.319 LiF–LiCl–Li2CO3 ternary 1.381
transition temperatures of LiF–LiCl–Li2CO3 are 726.8 K, 727 K, 727.8 K,
ternary eutectic salt eutectic salt + 2 wt% as shown in Fig. 13 (b). This is in good agreement with the eutectic point
MWCNTs determined above. After 600 min, 1200 min and 1800 min tests, the
change of phase transition temperature can be ignored. The above re­
sults show that the designed LiF–LiCl–Li2CO3 eutectic salt has good
thermal stability.

5. Conclusion

In this study, the thermodynamic evaluation and calculation of the

LiF–LiCl–Li2CO3 subsystems were performed and the thermodynamic
model parameters were optimized and obtained, with the conclusions as
below.

(1) The eutectic composition of LiF–LiCl–Li2CO3 ternary system (735

K with compositions of XLiF = 28.41 mol%, XLiCl = 55.09 mol%
and XLi2CO3 = 16.50 mol%) was predicted.
(2) The thermophysical properties of LiF–LiCl–Li2CO3 ternary salt
and its CPCMs with different mass fraction of MWCNTs (0.2 wt%,
0.5 wt%, 1 wt%, 2 wt%) were studied. The melting temperature,
phase change latent heat, thermal diffusivity, thermal conduc­
tivity and upper limit of thermal stability were measured and
analyzed. The following conclusions have been drawn:
(a) The melting temperatures of CPCMs have negligible change
Fig. 11. Thermal conductivity of LiF–LiCl–Li2CO3 eutectic salt and its CPCMs. with MWCNTs.
(b) Addition of appropriate MWCNTs can increase the specific
heat capacity, the latent heat, thermal diffusivity and thermal
conductivity of LiF–LiCl–Li2CO3 by 33.33%, 23.53%, 11.00%
and 13.43%.
(c) The upper temperature limit of the thermal stability of
LiF–LiCl–Li2CO3 base salt and its CPCMs with MWCNTs are
above 923–1023 K, indicates the good thermal stability.

To sum up, the good thermophysical properties imply that the

designed eutectic salt has great potential in high-temperature TES sys­
tems. LiF–LiCl–Li2CO3 based CPCMs with 0.5 wt% MWCNTs exhibit the
best overall TES performance. It must be noticed that the costs of the LiF,
LiCl, Li2CO3 are relatively higher than commercial used salts, which
should be considered during the application of designed eutectic salt.

CRediT authorship contribution statement

Zeyang Kang: Conceptualization, Investigation, Methodology, Re­

sources, Writing – original draft. Jimin Xu: Data curation, Software. Hui
Liu: Investigation, Methodology. Yuwen Lin: Data curation, Method­
ology. Xiangyang Liu: Writing – review & editing, Visualization, Su­
pervision, Project administration, Conceptualization. Maogang He:
Fig. 12. Weight loss curves of base salt and CPCMs during heating process.

Table 5
temperature of 923 K. It means that LiF–LiCl–Li2CO3 eutectic salt and its Weight loss of LiF–LiCl–Li2CO3 after 600 min, 1200 min, 1800 min.
CPCMs can work at 923 K.
After 600 min After 1200 min After 1800 min
The stability of LiF–LiCl–Li2CO3 eutectic salt were also studied by
thermal cycling and thermal shock experiments in this work. In the Weight loss in muffle furnace 0.46% 0.47% 0.47%

7
Z. Kang et al.
Fig. 13. TG and DSC curves of base salt after 600 min, 1200 min, 1800 min at
923 K.
Conceptualization, Funding acquisition, Project administration, Writing
– review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The supports which are provide by the National Natural Science
Foundation of China (No.51936009 and No. 51721004) for the
completion of this work are gratefully acknowledged.
References
[1] Z. Rong, G. Pan, et al., Ab-initio molecular dynamics study on thermal property of
NaCl-CaCl2 molten salt for high-temperature heat transfer and storage, Renew.
Energy 163 (2021) 579–588.
[2] Z. Ma, M. Li, et al., Effects of partly-filled encapsulated phase change material on
the performance enhancement of solar thermochemical reactor, J. Clean. Prod. 279
(2020), 123169.
8
Solar Energy Materials and Solar Cells 241 (2022) 111744
[3] G. Pan, X. Wei, et al., Thermal performance of a binary carbonate molten eutectic
salt for high-temperature energy storage applications, Appl. Energy 262 (2020),
114418.
[4] L. Du, J. Ding, et al., Thermal properties and thermal stability of the ternary
eutectic salt NaCl-CaCl2-MgCl2 used in high-temperature thermal energy storage
process, Appl. Energy 204 (2017) 1225–1230.
[5] S. Wu, H. Peng, et al., Design and investigation of the novel ZnCl2 based ternary
chloride salts with low-temperature for sensible energy storage, Appl. Therm. Eng.
171 (2020), 114917.
[6] X. Li, S. Wu, et al., Experimental investigation and thermodynamic modeling of an
innovative molten salt for thermal energy storage (TES), Appl. Energy 212 (2018)
516–526.
[7] Z. Li, Y. Lu, et al., Applications and technological challenges for heat recovery,
storage and utilisation with latent thermal energy storage, Appl. Energy 283
(2021), 116277.
[8] I. Barin, O. Knacke, et al., Thermochemical Properties of Inorganic Substances,
Second-ed., Springer-Verlag, Berlin, 1977.
[9] L. Qiu, Y. Ouyang, et al., Review on micro/nano phase change materials for solar
thermal applications, Renew. Energy 140 (2019) 513–538.
[10] J. Gasia, L. Miro, et al., Review on system and materials requirements for high
temperature thermal energy storage. Part 1: general requirements, Renew. Sustain.
Energy Rev. 75 (2017) 1320–1338.
[11] H. Nazir, M. Batool, et al., Recent developments in phase change materials for
energy storage applications: a review, Int. J. Heat Mass Tran. 129 (2019) 491–523.
[12] C. Liu, Z. Rao, et al., Review on nanoencapsulated phase change materials:
preparation, characterization and heat transfer enhancement, Nano Energy 13
(2015) 814–826.
[13] X. Wei, Y. Yin, et al., Preparation and enhanced thermal conductivity of molten salt
nanofluids with nearly unaltered viscosity, Renew. Energy 145 (2020) 2435–2444.
[14] Y. Tao, C. Lin, et al., Effect of surface active agent on thermal properties of
carbonate salt/carbon nanomaterial composite phase change material, Appl.
Energy 156 (2015) 478–489.
[15] Y. Tao, C. Lin, et al., Preparation and thermal properties characterization of
carbonate salt/carbon nanomaterial composite phase change material, Energy
Convers. Manag. 97 (2015) 103–110.
[16] Y. Yu, C. Zhao, et al., Superior thermal energy storage performance of NaCl-
SWCNT composite phase change materials: a molecular dynamics approach, Appl.
Energy 290 (2021), 116799.
[17] N.I. Ibrahim, F.A. Al-Sulaiman, et al., Heat transfer enhancement of phase change
materials for thermal energy storage applications: a critical review, Renew.
Sustain. Energy Rev. 74 (2017) 26–50.
[18] D. Han, B.G. Lougou, et al., Thermal properties characterization of chloride salts/
nanoparticles composite phase change material for high-temperature thermal
energy storage, Appl. Energy 264 (2020), 114678.
[19] H. Tian, L. Du, et al., Enhanced thermal conductivity of ternary carbonate salt
phase change material with Mg particles for solar thermal energy storage, Appl.
Energy 204 (2017) 525–530.
[20] F. Yuan, M. Li, et al., Specific heat capacity improvement of molten salt for solar
energy applications using charged single-walled carbon nanotubes, Appl. Energy
250 (2019) 1481–1490.
[21] C. Wang, K. Chen, J. Huang, et al., Thermal behavior of polyethylene glycol based
phase change materials for thermal energy storage with multiwall carbon
nanotubes additives, Energy 180 (2019) 873–880.
[22] G. Mohan, M. Venkataraman, et al., Assessment of a novel ternary eutectic chloride
salt for next generation high-temperature sensible heat storage, Energy Convers.
Manag. 167 (2018) 156–164.
[23] T. Delise, A.C. Tizzoni, et al., Technical and economic analysis of a CSP plant
presenting a low freezing ternary mixture as storage and transfer fluid, Appl.
Energy 265 (2020), 114676.
[24] T. Delise, A.C. Tizzoni, et al., Phase diagram predictive model for a ternary mixture
of calcium, sodium, and potassium nitrate, ACS Sustain. Chem. Eng. 8 (2020)
111–120.
[25] O. Redlich, A.T. Kister, Algebraic representation of thermodynamic properties and
the classification of solutions, Ind. Eng. Chem. 40 (1948) 345–348.
[26] C.W. Bale, E. Belisle, P. Chartrand, et al., FactSage thermochemical software and
databases, 2010-2016, Calphad Comput. Coupling Phase Diagrams Thermochem.
55 (2016) 1–19.
[27] Y. Liu, Z. Tang, et al., Insight into effects of molten KNO3-NaNO2-NaNO3
volumetric absorption of solar radiation from different factors by absorption
spectroscopy, J. Mol. Liq. 301 (2020), 110604.
[28] F. Yuan, M. Li, et al., A novel model for predicting the effective specific heat
capacity of molten salt doped with nanomaterial for solar energy application, Appl.
Therm. Eng. 195 (2021), 117129.
[29] Z. Jiang, A. Palacios, et al., Novel key parameter for eutectic nitrates based
nanofluids selection for concentrating solar power (CSP) systems, Appl. Energy 235
(2019) 529–542.
[30] C. Villada, A. Bonk, et al., High-temperature stability of nitrate/nitrite molten salt
mixtures under different atmospheres, Appl. Energy 226 (2018) 107–115.
[31] Z. Zhang, Y. Yuan, et al., Thermophysical properties enhancement of ternary
carbonates with carbon materials for high-temperature thermal energy storage,
Sol. Energy 155 (2017) 661–669.
[32] Y. Xiong, Z. Wang, et al., Performance enhancement of bromide salt by nano-
particle dispersion for high-temperature heat pipes in concentrated solar power
plants, Appl. Energy 237 (2019) 171–179.
Z. Kang et al.
[33] J. Zeng, Z. Cao, et al., Effects of MWNTs on phase change enthalpy and thermal
conductivity of a solid-liquid organic PCM, J. Therm. Anal. Calorim. 95 (2009)
507–512.
[34] T. Zhang, M. Wang, et al., Improving thermal energy storage and transfer
performance in solar energy storage: nanocomposite synthesized by dispersing
nano boron nitride in solar salt, Sol. Energy Mater. Sol. Cell. 232 (2021), 111378.
[35] P. Cheng, X. Chen, et al., Different dimensional nanoadditives for thermal
conductivity enhancement of phase change materials: fundamentals and
applications, Nano Energy 85 (2021), 105948.
[36] X. Chen, P. Cheng, et al., Carbon-based composite phase change materials for
thermal energy storage, transfer, and conversion, Adv. Sci. 8 (2021), 2001274.
Solar Energy Materials and Solar Cells 241 (2022) 111744
[37] A. Awad, H. Navarro, et al., Thermal-physical properties of nanoparticle-seeded
nitrate molten salts, Renew. Energy 120 (2018) 275–288.
[38] G.J. Janz, C.B. Allen, et al., Physical Properties Data Compilations Relevant to
Energy Storage, II. Molten Salts: Data on Single and Multicomponent Salt Systems,
NSRDS-NBS 61 Part II, National Bureau of Standards, 1979.
[39] C. Masarapu, Y. Henry, et al., Specific heat of aligned multiwalled carbon
nanotubes, Nanotechnology 16 (2005) 1490–1494.
[40] P.D. Myers, T.E. Alam, et al., Nitrate salts doped with CuO nanoparticles for
thermal energy storage with improved heat transfer, Appl. Energy 16 (2016)
225–233.